Detergent compositions containing oxydisuccing acid salts as builders

ABSTRACT

There are disclosed herein detergent compositions containing a water-soluble organic detergent compound and as a builder therefore the normal alkali metal, ammonium or alkanol amine salts of ether polycarboxylic acids selected from the group consisting of oxydisuccinic acid, carboxymethyloxysuccinic acid and hydrofuran tetracarboxylic acid.

United States Patent Lamberti et al.

[ Jan. 18,1972

[s41 DETERGENT COMPOSITIONS CONTAINING OXYDISUCCING ACID SALTS AS BUILDERS [72] Inventors: Vincent Lamberti, Upper Saddle River;

Mark D. Konort, Haworth, both of NJ.

Lever Brothers Company, New York, N.Y.

[22] Filed: Nov. 24, 1969- [21 Appl. No.: 879,627

Related US. Application Data [63] Continuation-impart of Ser. No. 731,700, May 24,

1968, abandoned.

[73] Assignee:

[52] US. Cl ..252/152, 252/89, 252/132, 252/135, 252/137, 252/175, 260/346.8

[51] Int. Cl ..Clld 3/20, C1 1d 7/26, C02b H22 [58] Field ofSearch ..252/89, 152, 156, 351, 132, 252/135, 175; 260/3468 Primary Examiner-Leon D. Rosdol Assistant Examiner-Dennis L. Albrecht Attameyl.ouis F. Kline, Jr., Melvin l-l. Kurtz and Edgar E. Ruff [5 7] ABSTRACT There are disclosed herein detergent compositions containing a water-soluble organic detergent compound and as a builder therefore the normal alkali metal, ammonium or alkanol amine salts of ether polycarboxylic acids selected from the group consisting of oxydisuccinic acid, carboxymethyloxysuccinic acid and hydrofuran tetracarboxylic acid.

7 Claims, No Drawings DETERGENT COMPOSITIONS CONTAINING OXYDISUCCING ACID SALTS AS BUILDERS This application is a continuation-in-part of application Ser. No. 731,700, filed May 24, 1968 now abandoned.

The present invention relates to detergent compositions containing a novel builder therefor.

Eutrophication is the process of enrichment of waters with nutrients, such as carbon, nitrogen, phosphorous, potassium, iron, trace metals and vitamins. Factors in the eutrophication monoisopropanolarnine salt of oxydisuccinic acid, the normal of lakes, streams and estuaries are natural runoff, agricultural drainage, ground water, precipitation, sewage and waste effluents.

Although there is no present adequate proof, it has been postulated that the phosphorous-containing builders present in detergent compositions can be a factor in eutrophication. Therefore any substitutes which do not contain phosphorous may decrease to some extent of eutrophication.

It is, therefore, an object of the present invention to provide detergent compositions with a builder compound which is free of phosphorus.

The compositions of the invention necessarily include both a synthetic builder and a water-soluble organic detergent compound. Such detergent compounds that are useful in the present invention are the anionic (soap and nonsoap), nonionic, zwitterionic and ampholytic compounds. The chemical nature of these detergent compounds is not an essential feature of the present invention. Moreover, such detergent compounds are well known to those skilled in the detergent art and the patent and printed literature are replete with disclosures of such compounds. Typical of such literature are Surface Active Agents by Schwartz and Perry and Surface Active Agents and Detergents by Schwartz, Perry and Berch, the disclosures of which are incorporated by reference herein.

The phosphorous-free builder for the detergent compositions of the invention are the normal alkali metal, ammonium and lower mono-, diand trialkanolamine salts of ether polycarboxylic acids selected from the group consisting of oxydisuccinic acid, carboxymethyloxysuccinic acid and hydrofuran tetracarboxylic acid. The oxydisuccinic acid and the hydrofuran tetracarboxylic acid are also known as 2,2 '-oxydisuccinic acid and tetrahydrofuran 2,3,4,5,-tetracarboxylic acid respectively.

The builder salts of the ether polycarboxylic acids of the present invention can be generally represented as follows:

wherein A is CI-l or when taken together with B to complete a heterocyclic ring is -CH; B is H, CH COOM or when taken together with A to complete a heterocyclic ring is CHCOOM and M is selected from the group constituting of alkali metals, ammonium, morpholinium and alkanol ammonium.

It is apparent that when A is taken together with B to complete the heterocyclic bond, B must be CHCOOM. The.

compound will then be the hydrofuran tetracarboxylate which can generally be represented as follows:

MOOC-C C-OOOM MOOC-CH HC-CO0M diisopropanolamine salt of oxydisuccinic acid, monosodium tripotassium oxydisuccinate, disodium dipotassium oxydisuccinate, trisodium monopotassium oxydisuccinate, the normal morpholine salt of oxydisuccinic acid, tetrasodium hydrofuran tetracarboxylate, tetrapotassium hydrofuran carboxylate, tetralithium hydrofuran carboxylate, tetraammonium hydrofuran tetracarboxylate, the normal monoethanolamine salt of hydrofuran tetracarboxylic acid, the normal diethanolamine salt of hydrofuran tetracarboxylic acid, the normal triethanolamine salt of hydrofuran tetracarboxylic acid, the normal monoisopropanolarnine salt of hydrofuran tetracarboxylic acid, the normal diisopropanolamine salt of hydrofuran tetracarboxylic acid, the normal triisopropanolamine hydrofuran tetracarboxylate, monosodium tripotassium hydrofuran carboxylate, disodium dipotassium hydrofuran tetracarboxylate, trisodium monopotassium hydrofuran tetracarboxylate, the normal morpholine salt of hydrofuran tetracarboxylate, trisodium carboxymethyloxysuccinate, tripotassium carboxymethyloxysuccinate, trilithium carboxymethyloxysuccinate; triammonium carboxymethyloxysuccinate, the normal monoethanolarnine salt of carboxymethyloxysuccinic acid, the normal diethanolarnine salt of carboxymethyloxysuccinic acid, the normal triethanolamine salt of carboxymethyloxysuccinic acid, the normal monoisopropanolarnine salt of carboxymethyloxysuccinic acid, the normal diisopropanolamine salt of carboxymethyloxysuccinic acid, monosodium dipotassium carboxymethyloxysuccinatc, disodium monopotassium carboxymethyloxysuccinate, the normal morpholinium salt of carboxymethyloxysuccinic acid, and the like.

The weight ratio of oxydisuccinate, carboxymethyloxysuccinate or hydrofuran tetracarboxylate builders to detergent compound ranges generally from about 1:3 to about [0:1 and more usually from about 2: l to about 5:1.

The oxydisuccinate, carboxymethyloxysuccinate and hydrofuran tetracarboxylate builders can be used either as the sole builder, where desired, can be used in conjunction with other well-known builders, examples of which include tetrasodium and tetrapotassium pyrophosphate, pentasodium and pentapotassium tripolyphosphate, trisodium and tripotas. sium nitrilotriacetate, starch or cellulose derived polycarboxylates, and the like. Other material which may be present in the detergent compositions of the invention in minor amounts are those conventionally present therein. Typical examples thereof include the well-known soil suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, fillers, optical brighteners, enzymes, suds boosters, suds depressants, germicides, antitamishing agents, cationic detergents and softeners and the like. The balance of the detergent compositions is water.

The detergent compositions of the present invention may be in any of the usual physical forms for such compositions, such as powders, beads, flakes, bars, tablets, liquids, pastes and the like. The compositions are prepared and utilized in the conventional manner. The wash solutions thereof desirably have a pH from about 7 to about 12, preferably from about 9 to about 11. At pH values below about 8.6 some of the salts of the oxydisuccinic acid, carboxymethyloxysuccinic acid and hydrofuran tetracarboxylic acid will be present in the acid salt form and some in the normal salt form.

The normal oxydisuccinate builder salts can be prepared in the conventional manner. Thus, the tetrasodium oxydisuccinate may be prepared as follows: An aqueous solution containing 5 grams of oxydisuccinic acid or 2,2'-oxydisuccinic acid in 35 ml. of distilled water is titrated to a pH of 7.5 with 42 ml. of a 2 N sodium hydroxide solution. The aqueous solvent is removed under reduced pressure and the residue is mainly tetrasodium oxydisuccinate or tetrasodium 2,2-oxydisuccinate. Similarly using carboxymethyloxysuccinic acid and the required amount of sodium hydroxide, the trisodium carboxymethyloxysuccinate can be prepared.

Employing a procedure similar to that given above, the corresponding norrnal alkali metal, ammonium and lower alkanol amine salts of oxydisuccinic acid and carboxymethyloxysuccinic acid can be prepared by using a stoichiometric quantity of the appropriate alkaline reactant. The normal mixed salts of oxydisuccinic acid and carboxymethyloxysuccinic acid can be prepared by neutralizing oxydisuccinic acid or carboxymethyloxysuccinic acid respectively with the requisite proportional amounts of basic compounds containing the desired cations.

The normal hydrofuran tetracarboxylate builder salts can be prepared in the conventional manner. Thus, the tetrasodium hydrofuran tetracarboxylate may be prepared as follows: The acid form of hydrofuran tetracarboxylic acid is available commercially. The sodium salt is prepared by dissolving the acid in a slight excess of dilute NaOH. Approximately 4 volumes of ethanol are added and the white precipitate was filtered. The precipitate is redissolved in water and similarly reprecipitated three more times. After the final precipitation the salt is dried in a vacuum oven at 105 C. Titration of a sample with perchloric acid in glacial acetic acid showed 100 percent tetrasodium hydrofuran tetracarboxylate.

The tetrasodium salt of hydrofuran tetracarboxylic acid does not have a melting point, but decomposes before melting. Differential thermal analysis of the material indicated that decomposition does not begin until over 400 C. (752 F.). Thus, this material is able to withstand high processing temperatures.

When the oxydisuccinic acid has been prepared in accordance with example l of US. Pat. No. 3,128,287 it has been found that a mixture of 2 diastereoisomeric forms of oxydisuccinic acid will be obtained. The less soluble form has been designated as the d,1-racemate. The more soluble diastereoisomer has been designated as the mesoform and is found in the aqueous filtrate after decomposition of the calcium salts with sulfuric acid and removal of the less soluble d,1- racemate. Accordingly, mixtures of meso and d,l-oxydisuccinate can be prepared as well as purified d,l-oxydisuccinic acid and a purified mesooxydisuccinic acid. Thus these materials may be prepared as follows:

Maleic anhydride, 19.6 g. (0.2 mole), is dissolved in 200 ml. water and heated to 100 C. for 5 minutes. Calcium hydroxide, 16.0 g. (0.22 mole), is then added and the mixture stirred and refluxed for 4 days. The insoluble calcium salts are filtered and dried. The dried product, 22 g., is slurried in water and passed through an Amberlite IR-12O cation exchange column to remove the calcium ions. The eluate is then evaporated to dryness to yield 14.5 g. of crude oxydisuccinic acid.

Meso/d, l -Oxydisuccinic Acids Eleven grams of crude oxydisuccinic acid obtained from the above example is digested with ml. of boiling acetone and filtered. The acetone extraction is repeated five more times to give a 60/40 mixture of meso/d,1-oxydisuccinic acid based on NMR analysis.

d,1-Oxydisuccinic Acid Oxydisuccinic acid prepared by the Pfizer procedure was purified by first recrystallizing twice from a minimum amount of water. The recrystallized product, g., was then dissolved in 600 ml. boiling water and flushed through an Amberlite lR-l20 cation exchange column to remove residual calcium cations. The eluate was then flash evaporated in vacuo to dryness. The residue was slurried with 100 ml. of acetone, filtered and further worked twice with 10 ml. portion of acetone. After vacuum drying, 18.2 g. of purified d,1-oxydisuccinic acid was obtained.

Examples of the detergent compositions of the invention are set forth below as illustrative but not limitive of such compositions.

EXAMPLES 14 The detergent formulations set forth in table l below (and in tables II-lX hereinafter) were prepared by blending together the recited components and were then tested for detergency or cleansing ability in the Terg-O-Tometer Test wherein the washing conditions were as follows (unless otherwise indicated): 65 percent Dacron35 percent cotton VCD (vacuum cleaner dust) cloth; F.; ppm. (2/1 Ca-H-/g-H-); 0.15 percent concentration of the total fonnulation in the washing solution; pH 9.5. (The pH of the washing solutions given herein was adjusted, where necessary, by the addition of caustic or sulfuric acid thereto.)

The average detergency units (DU) of the formulations is the final reflectance of the washed cloth minus the initial reflectance of the solid cloth (the average of two runs), the reflectance being measured with a Gardner Automatic Color Difference Meter, Model AC-3.

The following abbreviations have been used in the tables and examples: LAS is an anionic surfactant which is sodium linear alkyl (C -C secondary benzene sulfonate; Neodol 45-1 1 is a nonionic surfactant which is an adduct of a modified Oxo type C,.,C alcohol with an average of 11 moles of ethylene oxide; C -C HAMT is an ampholytic surfactant which is sodium hydroxyalkyl (C -C N- methyltaurate; (DCH) sulfobetaine is a zwitterionic surfactant which is cocodimethylsulfopropyl betaine NaODS is tetrasodium oxydisuccinate; STPP is pentasodium tripolyphosphate; TKPP is tetrapotassium pyrophosphate; NTA is trisodium nitrilotriacetate; RU silicate is a sodium silicate having a $10,: Na 0 ratio of 2.4:1; Na HFF C is tetrasodium hydrofuran tetracarboxylate; DU is detergency units; and the bal is balance.

TABLE 1 Percent by Weight The detergent (LAS) used in examples l-4 is representative of the water-soluble organic anionic detergent compounds. Comparative example 1, which contained only the organic anionic detergent compound, had low detergency of only 3.2 units. Comparative example 2, which contained only tetrasodium oxydisuccinate, also had low detergency of only 2.3 units. Comparative example 3, which contained the organic anionic detergent compound and pentasodium tripolyphosphate as a builder, had higher detergency of 22.5 units.

The remaining example 4 is representative of the detergent compositions of the invention. Example 4 contained the organic anionic detergent compound and tetrasodium oxydisuccinate as a builder. This composition had a high detergency of 19.5 units, which value compares favorably with that for comparative example 3 which contained the organic anionic detergent compound and phosphate builder. Thus, the detergent composition of example 4 has high detergency properties amounting to 87 percent of the standard detergent fonnulation of comparative example 3 (19.5/22.5X100=87 percent.)

EXAMPLES 5-8 Examples 5-8 presented in table 11 below contained a representative water-soluble organic nonionic detergent compound, namely Neodol 45-11, which has been identified above. These compositions were prepared and tested in the same manner as set forth above for examples 1-4 with the exception that the concentration of the total formulation in the washing solution was raised to 0.20 percent and the pH was Comparative examples 5 in table 11 above contained only the representative nonionic detergent compound and it had a detergency of only 16.6 units. Comparative example 6, which contained only tetrasodium oxydisuccinate, had a detergency of only 14.1 units. Comparative example 7 contained pentasodium tripolyphosphate as a builder in addition to the nonionic detergent compound. This formulation had higher detergency of 26.5 units.

Example 8, which is representative of the detergent compositions of the invention, contained in addition to the nonionic detergent compound, tetrasodium oxydisuccinate as the builder. This formulation had increased detergency of 26.1 units showing again that the tetrasodium oxydisuccinate functions quite satisfactorily as a builder and it is comparable in regard thereto to the phosphate builder. Thus, the formulation of example 8 has excellent detergency properties amounting to 99 percent of the standard detergent formulation of comparative example 7 (26.1/26.5X100=99 percent.)

EXAMPLES 9-12 Examples 9-12 presented in table Ill below contained a representative water-soluble organic ampholytic detergent compound identified above. The compositions were prepared and tested in the same manner as set forth in examples 1-4 except the concentration of the total formulation in the washing solution was 0.20 percent and the pH was 9.6.

TABLE 111 Percent by Weight Example No. 9 10 11 c,,-c,. HAMT NaODS STPP Water Average Detergency Units (DU) bal bal

26.9 units.

Example 12, which is a composition of the invention. contained the ampholytic detergent compound and tetrasodium oxydisuccinate as the builder. 1t is seen that the formulation of example 12 has excellent detergency properties amounting to 96 percent of the standard detergent formulation of comparative example 11 (25.9/26.9 100=96 percent.) Thus, example 12 further establishes that the tetrasodium oxydisuccinate functions as a detergency builder and it is comparable in that regard to the phosphate builders.

EXAMPLES 13-16 Examples 13-16 given in table 1V below contained a representative water-soluble organic zwitterionic detergent compound identified above. These compositions were prepared and tested in the same manner as set forth in examples 5-8.

TABLE [V Percent by Weight Units (DU) Comparative examples 13 in table IV above, which contained only the representative zwitterionic detergent compound, had a detergency of only 13.5 units. Comparative example 14 contained only tetrasodium oxydisuccinate and had a detergency of only 13.0 units. Comparative example 15, which contained the zwitterionic detergent compound and pentasodium tripolyphosphate as a builder, had an increased detergency of 26.4 units.

Example 16, which is a representative composition of the invention, contained the zwitterionic detergent compound and tetrasodium oxydisuccinate as a builder. This formulation had a high detergency of 25.6 units. Thus, once again, the formulation of example 16 of the invention has excellent detergency properties amounting to 97 percent of that of the standard detergent formulation of comparative example 15 (25.6/26.4 E'=97 percent.)

EXAMPLES 17-20 The fonnulations of examples 17-20 in table V below differ from the preceding examples 1-16 in that they further contained sodium silicate as a buffer. These compositions were prepared and tested as set forth in examples 1-4 except the hardness of the wash water was at three varying concentrations, namely 50 ppm, p.p.m. and 360 p.p.m.; the con centration of the total formulation in the washing solution was 0.20 percent; and the pH was 10.0.

TABLE V Percent by Weight In table V above, examples 17 and 18 are comparative formulations for examples 19 and 20 respectively of the invention. It will be noted from the data therein that the zwitterionic detergent formulation containing tetrasodium oxydisuccinate (example 19) and the nonionic detergent formulation containing tetrasodium oxydisuccinate (example 20) maintained high detergency properties over the wide hardness range tested relative to their comparative formulations (examples 17 and 18 respectively). Thus, example 19 of the invention had excellent detergency properties amounting to 93 percent at 50 p.p.m., 88 percent at 180 p.p.m. and 85 percent at 360 p.p.m. of that of the standard comparative detergent formulation of example 17, while example 20 of the invention also had excellent detergency properties amounting to 95 percent at 50 p.p.m., 87 percent at 180 p.p.m., and 88 percent at 360 p.p.m. of that of the standard comparative detergent formulation of example 18.

EXAMPLES 21-23 These three examples illustrate the effectiveness of tetrasodium oxydisuccinate as a detergency builder when used in combination with either an inorganic builder (STPP) or an organic builder (NTA). These compositions were prepared and tested in the same manner as set forth for examples 17-20 except they were tested at 180 p.p.m. hardness only.

In table VII above, examples 24 and 25 are comparative formulations for examples 26 and 27 respectively of the invention. In comparing the data for example 26 with that for example 24, it will be noted that the formulation of the invention of example 26 has excellent detergency on both of the additional soil cloths amounting to 95 percent (cotton VCD) and 99 percent (FDS) of the comparative standard detergent fonnulation of example 24. The fonnulation of the invention of example 27 when compared with comparative standard detergent formulation 25 also shows excellent detergency properties on cotton VCD cloth amounting to (94 percent of that of the standard detergent formulation of comparative example 25. On the FDS cloth, however, the detergent fonnulation of the invention of example 27 shows a surprisingly high margin of superiority in detergency properties amounting to 123 percent of that of the standard comparative detergent formulation of example 25.

EXAMPLES 28-30 Examples 28-30 in table V111 below, like examples 21-23 in table V1 above, demonstrate the effectiveness of tetrasodium oxydisuccinate as a builder in detergent compositions when used in combination with an inorganic builder. These compositions of examples 28-30 were prepared and tested as set forth for examples 21-23.

TABLE VI TABLE VIII Percent by Weight Percent by Weight Example No. 21 22 23 No. 28 29 30 Ncodol 45-11 l0 l0 l0 sig I i Neodol 45-11 r0 r0 r0 so 15 1223 .2 I if. Water bal bal bal STPP 25 Average Detergency 25.3 25.2 26.3 w l b b Units atcr ba al al 40 Average Detcrgency 17.7 14.0 15.3

Units (DU) From the data set forth above in table VI, it will be noted that detergent compositions (examples 22 and 23) containing tetrasodium oxydisuccinate in combination with an inorganic builder (pentasodium tripolyphosphate) or in combination with an organic builder (trisodium nitrilotriacetate) have excellent detergency properties amounting to 100 percent and 104 percent of that of the standard detergent formulation of comparative example 21.

EXAMPLES 24-27 These four examples demonstrate the effectiveness of the detergent compositions of the invention in the cleansing of soil cloths other than the 65 percent Dacron35 percent cotton VCD soil cloth used in the preceding examples 1-23. Thus, in examples 24-27 two different further soil test cloths were used, namely, cotton VCD (vacuum cleaner dust) cloth and FDS (Foster D. Snell) soil test cloth. The compositions were prepared and tested as set forth in examples 21-23 except for the change in the soil test cloths.

From the data presented in table V111 above, it will be seen that if one-half of the tetrapotassium pyrophosphate (TKPP) is replaced by tetrasodium oxydisuccinate (NaODS) (P r example 30), the detergency still amounts to 86 percent of that of the all TKPP formulation (comparative example 28). In comparison to the pentasodium tn'polyphosphate (STPP) comparative formulation of example 29, however, the tetrasodium oxydisuccinatetetrapotassium pyrophosphate combination of example 30 is superior with detergency amounting to 109 percent of that of the formulation of example 29 (15.3/17.7 l00=86 percent and 15.3/14.0 l00=109 percent).

EXAMPLES 3 1-3 3 Examples 31-33 in table 1X below are illustrative of the utilization of tetrasodium oxydisuccinate in combination with an organic builder in detergent compositions and hence these examples constitute an extension of examples 21-23 in table V1 and examples 28-30 in table V111. These three formulations were prepared and tested in the same manner as set forth for examples 21-23.

TABLE 1X Percent by Weight Example No. 31 32 33 Neodol 45-11 10 10 I0 NaODS 2S NTA 50 25 STPP 50 Water but be! bal Average Detergency 25.3 24.5 24.] Units (DU) From the data set forth in table IX above, it is seen that a nonionic detergent formulation containing trisodium nitrilotriacetate as the organic builder (comparative example 31) has excellent detergency amounting to 103 percent of that of the standard comparative detergent formulation of example 32 (25.3/24.5X100=103 percent). Replacement of one-half of the trisodium nitrilotriacetate by tetrasodium oxydisuccinate (example 33 of the invention) lowers the detergency only slightly to 98 percent of that of the standard comparative detergent formulation of example 32 (24.l/24.5Xl=98 percent).

Results similar to those presented hereinabove are achieved when the normal oxydisuccinate salt is other than tetrasodium oxydisuccinate, such as the other normal oxydisuccinate salts set forth hereinabove, and when the detergent compositions contain further conventional additives.

MESO/d,l AND d,l-OXYDISUOOINIC ACIDS AS DETERGENT BUILDERS FOR LAS EXAMPLES 34-37 No'rE.-Washing Conditions=Terg-O-Tometer detergency; daeron/ Percent eflidency Percent DU for DU for compared Example N 0. builder NaHFTC BTPP with STPP 32. 2 39 g g i (98) 49 3112 31.2 i (101) 29. 8 29. lo 41 0{ fig 3 (101) 42 1o{ 2&0 (109) 43 0 DU=14.9, 14.1

l5 Formulation (0.15%) as above, with no RU silicate NaHFlC As A Detergent Builder For LAS: Detergency vs.

cotton VCD cloth; 120 F.; 180 p.p.m. (2:1 Ca++/Mg++); 0.2% conwater Hardness centration of total formulation; pH=l0.0.

Formulation (percent) EXA P E 47 50 34 35 36 37 Component: 30 C/ D-VCD Soil ClOthS Tetrasodium salt of 60/40 meso/d,1- v V oxydisuccinic acid 50 Tetrasodium salt of d,l-oxydisuccinic 50 l 0 157 a Formu ation 0 Tetrasodium salt of unpuritied d,l-

oxydisuccinic acid and (Pfizer procedure) 50 3 5 Sodium tr 50 20% LAS RU silicate solid 10 10 i0 10 10% Ru Silicate LAS 18 18 18 8 20% MMSO4 Water Balance 50% Builder Average detergency units (D U) 26. 4 26. 7 26.2 26. 9 Percent efficiency vs. control, formulation #37 .1 99 97 NaHFIC As A Detergent Builder For LAS: Detergency vs.

Concentration H 6 53 er e ency EXAMPLES 38-46 ness DU for DU for compared C/V VCD Soil Cloths 1 0 p'pm- Hadness Example No. p.p.m. NaHFTC STPP with S'IPP 0 36. 5 37. 3 (98) Formulation (0.15%) 90 {gig (93) 20% LAS 18D g g (96) 10% RU Silicate 4 5 20% N315). 300 {27: 0 v (92) O%% Builder NaIIFTC AS A DETERGENT BUILDER FOR VARIOUS SURFAC'IAN'IS, 180 P.P.M. HARDNESS-EXAMPLES 51-59 Formulation I (0.16%:

Active LAS, HAMT, or DCH 10%RU silicate 20% N 112804 40% builder Formulation II (0.20%):

Neodol 45-11 10% RU silicate 20% Na2SO4 40% builder Percent etliciency DU for D U for com ared Example N 0. Active Soil cloth NaHFIO STPP with 'IPP 51. LAS CID-VCD 32. 2 32. 8 (98) 31. 8 32. 7 Neodol C/DVCD 29. 0 31. 4 (89) 26.8 31. 4 .410 27.1 29. l (91) ll. 29. 2 30. B (06) 24. 7 27. 3 (00) 22. 6 23. 7 (95) 12.8 14. 3 (00) 12.2 15. 1 (Si) 14. 7 16. 4

l Formulation contains no RU silicate. 2 A commercially available soil cloth.

TRISODIUM CARBOXYMETHYLOXYSU CCINATE AS A DETERGENT BUILDER-EXAMPLES 65-74 NOTE .Washing Conditions-Terg-O-Tometer; dacron/cotton VCD cloth; 120 F.; 180 ppm. (2:1 Ca++[Mg++); 0.20% concentration of total formulation for Examples 65 and 66; 0.25% concentration for Examples 67 to 74; pH=10.0.

Formulation (percent) Component:

'Irlsodium salt of carboxymethyloxysuocinie acid. 60 50 50 50 50 Sodium tripolyphosphate 50 50 60 50 10 10 10 10 10 RU Silicate solids alan Average detergency (DUs) Percent etficiency vs. control formulation 1 NaHFTC As A Detergency Builder in Mixtures with NTA What is claimed is:

l. A detergent composition consisting essentially of: Examples 6044 A. A water-soluble organic detergent selected from the groups consisting of anionic, nonionic, zwitterionic and CID-1CD Sod Cloths 180 Hardness ampholytic surfactants, and mixtures thereof; and

Formulation (0 15%) B. A detergent builder selected from the group consisting of alkali metal, ammonium, morpholinium and alkanol am- 20% LAS monium salts of oxydisuccinic acid, and mixtures thereof, :3: fi g the weight ratio of said builder salt to organic detergent 40% a ranging from about 1:3 to 10:1.

2. The detergent composition as defined by claim 1 wherein the weight ratio of the builder salt to detergent ranges from about 2:1 to about 5:1.

3. The detergent composition as defined by claim 1 wherein the oxydisuccinate is tetrasodium oxydisuccinate. NTA/ 52332; 4. The detergent composition as defined by claim 1 wherein il er DU for mp r the oxydlsucclnate 1S tetrapotassium oxydlsuccinate. Example NaHFTC with STPP 5. The detergent composition as defined by claim 1 wherein 6O :0 34. 5 (105) the oxydisuccinate is tetralithium oxydisuccinate.

3010 Z (98) 6. The detergent composition as defined by claim 1 wherein 20: 32. 2 (97) 40 l the oxydisuccinate is tetraammonium oxydisuccinate. 10:30 gig (97) 7. The detergent composition as defined by claim 1 wherein 0:40 31. 8 (98) the oxydisuccinate is disodium dipotassium oxydisuccinate.

NOTE.DU (40% SV'IPP) 328, 32.7. 77

EDWARD M.FLETCHER JR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORECTION Patent No. 3,635,830 Dated January 18, 1972 hlincent Lambert et al It is certified that errorappears .in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Covervpage, title, OXYDISUCCING" should read OXYDISUCCINIC-' Cover page, inventors, add -Ira Weil, New York, New York-.

Column 1 line 2 "OXYDISUCCING" should read --OXYDISUCCINIC- Signed and sealed this 1st day of August 1972.

(SEAL) 'Attest:

ROBERT GO'I'TSCHALK Attesting Officer Commissioner of Patents FORM PO-105O (10-69) USCOMM-DC scenes9 U.S. GOVERNMENT PRINTING OFFICE: I969 0-356-334 

2. The detergent composition as defined by claim 1 wherein the weight ratio of the builder salt to detergent ranges from about 2:1 to about 5:1.
 3. The detergent composition as defined by claim 1 wherein the oxydisuccinate is tetrasodium oxydisuccinate.
 4. The detergent composition as defined by claim 1 wherein the oxydisuccinate is tetrapotassium oxydisuccinate.
 5. The detergent composition as defined by claim 1 wherein the oxydisuccinate is tetralithium oxydisuccinate.
 6. The detergent composition as defined by claim 1 wherein the oxydisuccinate is tetraammonium oxydisuccinate.
 7. The detergent composition as defined by claim 1 wherein the oxydisuccinate is disodium dipotassium oxydisuccinate. 